EP1321441B1 - Verre et pâte conductrice l'utilisant - Google Patents

Verre et pâte conductrice l'utilisant Download PDF

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Publication number
EP1321441B1
EP1321441B1 EP02027616A EP02027616A EP1321441B1 EP 1321441 B1 EP1321441 B1 EP 1321441B1 EP 02027616 A EP02027616 A EP 02027616A EP 02027616 A EP02027616 A EP 02027616A EP 1321441 B1 EP1321441 B1 EP 1321441B1
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EP
European Patent Office
Prior art keywords
glass
conductive paste
group
total
resistance
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Expired - Lifetime
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EP02027616A
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German (de)
English (en)
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EP1321441A1 (fr
Inventor
Tetsuya Tanaka
Kenji Morinaga
Mikio Yamazoe
Megumi Kawahara
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Shoei Chemical Inc
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Shoei Chemical Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates to a conductive paste suitable for forming electrodes of electronic components and conductors of thick-film circuits and to a glass used therein. More particularly, the present invention relates to a conductive paste that can be fired even in a non-oxidizing atmosphere and is suitable for forming terminal electrodes of multilayer ceramic components using a base metal such as nickel or copper for inner electrodes and to a glass used therein.
  • Multilayer ceramic components such as multilayer capacitors, multilayer inductors, and the like are typically fabricated in the manner as follows. Unfired (green) ceramic sheets, for example, of a dielectric or magnetic material are alternately laminated with a plurality of inner electrode paste layers to obtain a non-fired laminate. Then, the laminate is cut and fired at a high temperature to obtain a ceramic body (referred to as "ceramic body” hereinbelow).
  • the firing has been conducted at a peak temperature of about 700-900°C in a non-oxidizing atmosphere, for example, an inert gas atmosphere or a reducing atmosphere, such as nitrogen or hydrogen-nitrogen and the like.
  • a non-oxidizing atmosphere for example, an inert gas atmosphere or a reducing atmosphere, such as nitrogen or hydrogen-nitrogen and the like.
  • a non-reducible glass which is stable even in firing under a non-oxidizing atmosphere has to be used as an inorganic binder for a conductive paste to be fired in the non-oxidizing atmosphere.
  • a PbO component contained in lead-containing glass frits, which have been widely used for conductive pastes, is easily reduced. Moreover, because lead is hazardous to the human bodies and causes environmental pollution, a glass containing no lead is required.
  • a glass which has not only a high adhesive strength, but also good resistance to acids so that the glass is not vulnerable to attack from acidic plating solutions.
  • binder removal Another problem is that because firing is conducted under an atmosphere with a small content of oxygen, organic components such as solvents and binder resins which are used as vehicles are difficult to oxidize and decompose. If sufficient burning, decomposition, removal (referred to as “binder removal” hereinbelow) are not conducted, the vehicle decomposition products are encapsulated in the film and/or partly become carbon and remain in the film. Those carbonaceous residues cause a variety of problems, such as preventing sintering, lowering the density of the resultant fired film due to pores formed by oxidation and gasification at a high temperature and decreasing the strength of the ceramics such as barium titanate constituting the ceramic body. The selection of inorganic binder is also important in terms of resolving these problems associated with binder removal.
  • a barium-containing glass and a zinc-containing glass have been comprehensively studied as a reduction-resistant glass which has a high adhesive strength with a substrate and makes it possible to provide conductors with excellent characteristics.
  • base metal terminal electrodes of multilayer ceramic capacitors which use a reduction-resistant glass such as barium borate glass, barium zinc borate glass, barium zinc borosilicate glass, and the like (see US Patent No. 3,902,102).
  • a copper paste for terminal electrodes comprising a barium borosilicate glass see Japanese Patent Publication No. 5-234415
  • a copper paste for terminal electrodes comprising a zinc borosilicate glass of specific composition including alkali metal components and alkaline earth metal components see Japanese Patent Publication No. 59-184511
  • an aluminum strontium borosilicate glass for terminal electrodes see Japanese Patent Publication No. 9-55118.
  • barium-containing glass has an advantage of low softening temperature so that it can be fired at low-temperatures even if lead is not contained therein, it does not have a sufficient resistance to plating solutions and permits permeation of plating solution occurring during electroplating which reduces the adhesive strength with the ceramic body, causes cracking and fracturing of the ceramic body, induces a decrease in insulation resistance, and reduces reliability of the resultant multilayer products.
  • glass spots lumps or spots of glass
  • a zinc-containing crystallizable glass is generally known to form a reaction layer and thereby strongly adhere to the ceramic body and has excellent strength, thermal shock resistance, resistance to plating solutions, and resistance to water.
  • a glass typically has a high softening point.
  • a problem associated with a zinc borate glass or a zinc borosilicate glass of specific composition with a low softening point is that it is difficult to obtain a uniform glass film from these glasses because they have a narrow range of vitrification and are susceptible to phase separation.
  • they are crystallizable glasses flow characteristics and crystallization behavior in the firing process are difficult to control.
  • the temperature range in which firing can be conducted is narrow because of dependence on process conditions, in particular, because of significant variations in characteristics related to the firing atmosphere, firing temperature, and the like.
  • some ceramic body is also known to decrease the electrode strength.
  • the ceramic body is formed from a barium titanate ceramic dielectric with F characteristic specified by JIS (Japanese Industrial Standard) C6429 and C6422, which has a high dielectric constant
  • the zinc-containing crystallizable glass of the terminal reacts with the ceramic body in the interface zone therebetween, forming a homogeneous reaction layer, strongly adhering to the substrate and showing practically no deep permeation into the ceramic body.
  • JIS Japanese Industrial Standard
  • B characteristic specified by JIS i.e., a flat capacity - temperature characteristic
  • the ceramic body so degraded may be cracked or fractured when a stress causing the electrode film to peel off is applied to the capacitor, for example, in a peel strength test of terminal electrodes.
  • the capacitor mounted on a circuit substrate or the like has poor reliability. This is apparently due to the difference in microstructure between the ceramics; ceramics with F characteristic have a relatively homogeneous structure, whereas ceramics with B characteristic has a heterogeneous structure in which the grain boundary portions thereof have a reaction activity higher than that of crystal portions.
  • terminal electrodes with excellent peel strength could not be obtained on such barium titanate ceramics with B characteristic.
  • Yet another object of the present invention is to provide an excellent conductive paste especially suitable for forming terminal electrodes of multilayer ceramic capacitors.
  • Still another object of the present invention is to provide a conductive paste causing no degradation of ceramic bodies and exhibiting an excellent adhesive strength with respect to a variety of dielectric ceramic bodies, in particular, when used for terminal electrodes of multilayer ceramic capacitors.
  • the present invention provides a glass containing no lead and comprising, calculated as oxides: 40-60 wt.% ZnO, 15-35 wt.% B 2 O 3 , 1-16 wt.% SiO 2 , 1-10 wt.% Al 2 O 3 , 2-15 wt.% MnO 2 , and at least one selected from the group consisting of Li 2 O, Na 2 O and K 2 O in their total of 0.5-10 wt.%.
  • the present invention also provides a glass containing no lead and comprising, calculated as oxides: 40-60 wt.% ZnO, 15-35 wt.% B 2 O 3 , 1-16 wt.% SiO 2 , 1-10 wt.% Al 2 O 3 , 2-15 wt.% MnO 2 , at least one selected from the group consisting of Li 2 O, Na 2 O and K 2 O in their total of 0-5 wt.%, and at least one selected from the group consisting of MgO, CaO, TiO 2 , Cr 2 O 3 , ZrO 2 , Ta 2 O 5 , SnO 2 , and Fe 2 O 3 in their total of 0.1-5 wt.% (referred to hereinbelow as "the second glass of the present invention").
  • the present invention also provides a conductive paste comprising the above-specified glass and a conductive paste for forming terminal electrodes of multilayer ceramic components.
  • the glass in accordance with the present invention is a zinc borosilicate crystallizable glass having a low softening point within a range of 500-700°C and is characterized in that it forms a homogeneous glass in which firing hardly causes phase separation and in that it shows appropriate crystallization behavior and flow characteristic during firing a conductive paste containing such a glass.
  • Using the glass in accordance with the present invention as an inorganic binder of a conductive paste not only makes it possible to obtain excellent characteristics of fired films, but also decreases dependence on firing temperature and allows the firing to be conducted within a wide temperature range.
  • the above glass component reacts with some of ceramic body components on the interface with the ceramic body, for example, of a capacitor and the reaction products penetrate into the dielectric.
  • the presence of this reaction layer increases the adhesive strength of the electrodes and can prevent the occurrence of cracking in the ceramic body during plating or thermal shock test.
  • the second glass of the present invention contains at least one component selected from among MgO, CaO, TiO 2 , Cr 2 O 3 , ZrO 2 , Ta 2 O 5 , SnO 2 , and Fe 2 O 3 .
  • a conductive paste containing the second glass is applied to ceramics with F characteristic, the glass and ceramic body form a homogeneous reaction layer, whereas when the conductive paste is applied to ceramic bodies having portions with high reactivity, such as ceramic bodies made of ceramics with B characteristic, a terminal electrode with a high adhesive strength can be also formed without degrading the ceramic body strength.
  • composition range of the glass in accordance with the present invention will be described below.
  • symbol % will represent percent by weight, unless stated otherwise.
  • ZnO forms a glass network in cooperation with B 2 O 3 and also becomes a constituent of precipitated crystals. In addition, it improves adhesion strength with the substrate. The content outside the range of 40-60% is undesirable because softening point of the glass becomes too high. If the paste is fired at a high temperature in a non-oxidizing atmosphere, ZnO is usually easily sublimated and/or reduced under the effect of residual carbon. However, in accordance with the present invention, because the binder removal ability is very good, no such problem arises despite a high content of ZnO.
  • B 2 O 3 is a network-forming oxide and also used as a flux. If the content thereof is less than 15%, the glass is devitrified, and if the content is above 35%, the chemical resistance of the glass decreases significantly. It is preferred that ZnO and B 2 O 3 be mixed so the molar ratio thereof is 55 : 45 - 65 : 35.
  • SiO 2 is a network-forming oxide and produces an effect of expanding the vitrification range and an effect of improving chemical resistance.
  • the content of more than 16% is undesirable because the softening point becomes too high.
  • the preferred content is no more than 13%. It is desirable that the total content of B 2 O 3 and SiO 2 be no more than 40 wt.%.
  • the drawback of the ZnO-B 2 O 3 -SiO 2 glass of the above-described composition is that phase separation easily occurs therein.
  • Al 2 O 3 prevents such phase separation so that a homogeneous glass can be formed. As a result, process dependency can be reduced.
  • Al 2 O 3 improves chemical resistance. If the content of Al 2 O 3 is above 10%, softening point becomes too high and the glass is devitrified.
  • the preferred content of Al 2 O 3 is no more than 8%.
  • the Mn component is present in the glass with a valence of 2 or 3 and apparently has the following effect.
  • the valence changes causing release of oxygen which is then bonded to residual carbon originating from the vehicle present in the paste and drive off it as CO 2 to the outside of the film.
  • the Mn component also effects an increase in the reactivity of the glass with metallic copper. If the mixing quantity is less than 2%, calculated as MnO 2 equivalent, the effect is small, and if it is more than 15%, the glass is devitirified in the production process and stable glass cannot be obtained.
  • the preferred content is 2-10%.
  • At least one alkali metal oxide selected from among Li 2 O, Na 2 O, and K 2 O is a network-modifying oxide which decreases the softening temperature of the glass. If the content thereof exceeds 10%, the chemical resistance of the glass decreases significantly. This component also affects the precipitation of crystals and if the content is small, the crystals do not precipitate sufficiently. Further, the form of precipitated crystals can be changed by selecting the type of alkali metal oxide. When Li 2 O is used alone, needle crystals cannot be precipitated. Therefore, it is preferred that Na 2 O and/or K 2 O be used therewith. With certain compositions of dielectric used for the ceramic bodies, there is a risk of Na 2 O degrading the capacitor characteristic. In such cases, using Na 2 O should be avoided.
  • the second glass of the present invention comprising at least one component selected from among MgO, CaO, TiO 2 , Cr 2 O 3 , ZrO 2 , Ta 2 O 5 , SnO 2 , and Fe 2 O 3 , addition of the above-mentioned alkali metal oxides is not always required. Even when they are added, the total content is preferably within a range of 5% and below.
  • Introducing a small amount of a component selected from among MgO, CaO, TiO 2 , Cr 2 O 3 , ZrO 2 , Ta 2 O 5 , SnO 2 , and Fe 2 O 3 in the glass comprising the above-described components has an effect of changing the crystallization behavior and reactivity of the glass in the above-described manner and is especially effective in applications to ceramic bodies with B characteristic.
  • the desired effect cannot be obtained if those components are outside the range of a total content of 0.1-5%.
  • the glass in accordance with the present invention can additionally contain small amounts of other oxides within ranges which do not affect properties of the glass.
  • the glass in accordance with the present invention can be produced by a usual method comprising mixing the starting material compounds of the respective components, melting, rapidly cooling, and grinding and also by other methods such as a sol-gel method, a spray pyrolysis method, an atomization method, and the like. It is especially preferred that the glass be produced by a spray pyrolysis method because fine spherical glass particles of uniform size can be obtained and it is not necessary to conduct grinding when using the glass for a conductive paste.
  • Any vehicle prepared by dissolving or dispersing a resin binder that is usually employed, for example, an acrylic resin, cellulose, and the like, in an aqueous or organic solvent may be appropriately selected and used according to the object or intended use. If necessary, a plasticizer, a dispersant, a surfactant, an oxidizing agent, an organometallic compound, and the like can be added. No limitation is also placed on the mixing ratio of the vehicle, and the vehicle can be used in an appropriate amount allowing the inorganic components to be retained in the paste and depending on the intended use or coating method.
  • metal oxides, ceramics, and the like which are usually used may be added as other inorganic binders or additives.
  • the conductive paste in accordance with the present invention is especially suitable for the formation of terminal electrodes of multilayer ceramic components, such as multilayer capacitors, multilayer inductors, and the like, but it can be also used for forming electrodes on other electronic components, for forming conductor layers on multilayer ceramic substrates, or for forming thick-film conductors on ceramic substrates, for example, from alumina or the like.
  • Conductive pastes were prepared in the following manner by using the glass powders produced in Example 1. Each conductive paste was produced by blending 12 weight parts of the glass powder and 40 weight parts of a vehicle in which an acrylic resin was dissolved in terpineol with 100 weight parts of a copper powder and mixing the components in a three-roll mill. The paste was then coated by a dipping method, so as to obtain a film thickness after firing of about 120 ⁇ m, on end surfaces of inner electrodes exposed from a fired ceramic body of a multilayer ceramic capacitor with a flat surface size of 3.2 mm x 1.6 mm which had been prepared using, as a dielectric, a ceramic comprising barium titanate as a main component and having F characteristic specified by JIS and nickel as inner electrodes.
  • multilayer ceramic capacitors with sample numbers of 1 to 12 were produced by drying each body for 10 minutes at a temperature of 150°C in a hot-air drier, followed by firing for a total of 1 hour with a peak temperature retention time of 10 minutes at a peak temperature shown in Table 2 in a nitrogen atmosphere with an oxygen concentration of no more than 5 ppm by using a belt-type muffle furnace. Samples with numbers 11 and 12 are outside the range of the present invention.
  • Adhesive strength lead wires were soldered to two opposing terminal electrodes so as to be perpendicular to the electrode surface, both lead wires were pulled in the opposite directions with a strength measurement device, and the values at which the electrode portions have broken were determined.
  • Peel strength lead wires were soldered to two opposing terminal electrodes so as to be parallel to the electrode surface, both lead wires were pulled to the left and right by applying a force perpendicular to the electrode surface with a strength measurement device, and the values at which the electrode portions have broken were determined.
  • Table 2 clearly shows that the conductive paste using the glass in accordance with the present invention had excellent film density, high resistance to thermal shocks, and high adhesive strength and also demonstrated practically no changes in characteristics caused by firing temperature.
  • conductive pastes were prepared in the same manner as in Example 2. Each paste was then coated by a dipping method, so as to obtain a film thickness after firing of about 120 ⁇ m, on end surfaces of inner electrodes exposed from a fired ceramic body of a multilayer capacitor ceramic body with a flat surface size of 2.0 mm x 1.25 mm which had been prepared using, as a dielectric, a ceramic comprising barium titanate as a main component and having B characteristic specified by JIS standard and nickel as inner electrodes.
  • multilayer ceramic capacitors with sample numbers of 13 to 21 were produced by drying each body for 10 minutes at a temperature of 150°C in a hot-air drier, followed by firing for a total of 1 hour with a peak temperature retention time of 10 minutes at a peak temperature of 800°C in a nitrogen atmosphere with an oxygen concentration of no more than 5 ppm by using a belt-type muffle furnace.
  • the sample with numbers 21 is outside the range of the present invention.
  • the conductive paste using the second glass of the present invention demonstrated excellent adhesive strength and peel strength even with respect to a ceramic body of a ceramic dielectric with B characteristic.
  • the glass in accordance with the present invention has a low softening point, contains no hazardous components such as lead and the like, and demonstrates appropriate viscosity characteristic and crystallization behavior in a firing process.
  • a conductive paste using such a glass as an inorganic binder organic components can be completely removed and a dense conductor with excellent resistance to plating solutions, adhesive strength, resistance to thermal shocks, and reliability can be produced even in case of firing in a non-oxidizing atmosphere.
  • the paste shows little dependence of firing process conditions and electrodes with excellent and uniform characteristics can be formed even in firing within a wide temperature range.
  • the paste is used for forming terminal electrodes of multilayer ceramic components, a high terminal strength and peel strength are obtained regardless of the type of ceramic body and ceramic components with high reliability can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Conductive Materials (AREA)

Claims (6)

  1. Verre ne contenant pas de plomb et contenant, en pourcentages d'oxydes, 40 à 60% en poids de ZnO, 15 à 35% en poids de B2O3, 1 à 16% en poids de SiO2, 1 à 10% en poids de Al2O3, 2 à 15% en poids de MnO2 et au moins un oxyde choisi dans le groupe comprenant Li2O, Na2O et K2O pour un pourcentage total de ceux-ci de 0,5 à 10% en poids.
  2. Verre ne contenant pas de plomb et contenant, en pourcentages d'oxydes, 40 à 60% en poids de ZnO, 15 à 35% en poids de B2O3, 1 à 16% en poids de SiO2, 1 à 10% en poids de Al2O3, 2 à 15% en poids de MnO2, au moins un oxyde choisi dans le groupe comprenant Li2O, Na2O et K2O pour un pourcentage total de 0 à 5% en poids de ceux-ci, et au moins un oxyde choisi dans le groupe comprenant MgO, CaO, TiO2, Cr2O3, ZrO2, Ta2O5, SnO2 et Fe2O3, pour un pourcentage total de ceux-ci de 0,1 à 5% en poids.
  3. Pâte conductrice comprenant une poudre électriquement conductrice, un liant et une poudre du verre selon la revendication 1 ou la revendication 2.
  4. Pâte conductrice selon la revendication 3, dans laquelle la poudre électriquement conductrice comporte au moins une poudre choisie dans le groupe comprenant des poudres de cuivre, de nickel, de cobalt et d'un alliage ou d'un composite contenant au moins l'un de ces métaux.
  5. Pâte conductrice selon la revendication 3, dans laquelle la poudre électriquement conductrice comporte au moins une poudre choisie dans le groupe constitué par des poudres d'argent, de palladium et d'un alliage ou d'un composite contenant au moins l'un de ces métaux.
  6. Pâte conductrice servant à former une électrode terminale d'une pièce multicouche en céramique, dans laquelle la pâte conductrice est conforme à l'une quelconque des revendications 3 à 5.
EP02027616A 2001-12-21 2002-12-11 Verre et pâte conductrice l'utilisant Expired - Lifetime EP1321441B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001390611 2001-12-21
JP2001390611 2001-12-21
JP2002316884A JP4300786B2 (ja) 2001-12-21 2002-10-30 ガラスおよびこれを用いた導体ペースト
JP2002316884 2002-10-30

Publications (2)

Publication Number Publication Date
EP1321441A1 EP1321441A1 (fr) 2003-06-25
EP1321441B1 true EP1321441B1 (fr) 2004-11-17

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EP02027616A Expired - Lifetime EP1321441B1 (fr) 2001-12-21 2002-12-11 Verre et pâte conductrice l'utilisant

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US (1) US6841495B2 (fr)
EP (1) EP1321441B1 (fr)
JP (1) JP4300786B2 (fr)
KR (1) KR100487669B1 (fr)
CN (1) CN1223539C (fr)
AT (1) ATE282585T1 (fr)
DE (1) DE60201965T2 (fr)
TW (1) TW562781B (fr)

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KR100487669B1 (ko) 2005-05-03
US6841495B2 (en) 2005-01-11
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JP2003246644A (ja) 2003-09-02
DE60201965T2 (de) 2005-03-31
CN1223539C (zh) 2005-10-19
KR20030052996A (ko) 2003-06-27
CN1427421A (zh) 2003-07-02
US20030119653A1 (en) 2003-06-26
DE60201965D1 (de) 2004-12-23
EP1321441A1 (fr) 2003-06-25
TW562781B (en) 2003-11-21
ATE282585T1 (de) 2004-12-15

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